TECHNICAL FIELD
[0001] The present invention relates to a synthetic quartz glass for an optical member,
a process for producing the same and a method of using the same, particularly to a
synthetic quartz glass for an optical member, which shows high transmittance of vacuum
ultraviolet light having a wavelength of 165 nm or shorter, a process for producing
the same and a method of using the same.
BACKGROUND ART
[0002] In recent years, along with high integration of LSI, a technique for fine patterning
with a narrower line width has been required in the photolithographic technology,
and shortening of the wavelength of the light for exposure is being advanced. For
example, the light source for a lithographic stepper has been advanced from conventional
g-line (wavelength: 436 nm) or i-line (wavelength: 365 nm) to adopt a KrF excimer
laser (wavelength: 248 nm) or an ArF excimer laser (wavelength: 193 nm). Further,
as a light source for next generation where a finer patterning technique is required,
a fluorine laser (wavelength: 157 nm) is mentioned as a prospective candidate.
[0003] In an optical system using a KrF excimer laser or an ArF excimer laser as a light
source, a synthetic quartz glass is employed, since it is transparent over a wide
wavelength range from a near infrared region to a vacuum ultraviolet region, and it
is excellent in various properties such that the thermal expansion coefficient is
very small so that it is excellent in dimensional stability, and it has high purity.
However, a synthetic quartz glass having a large OH group content, which is used for
a KrF excimer laser or an ArF excimer laser, has a low transmittance in a region of
wavelengths of not longer than 165 nm, and as such, it is not useful for a fluorine
laser which is expected to be a light source of next generation.
[0004] Further, with a synthetic quartz glass having the OH group content reduced in order
to improve the transmittance in a region of wavelengths of not longer than 165 nm,
the transmittance sharply decreases as the wavelength of the transmitted light becomes
shorter than about 170 nm.
[0005] Accordingly, in a case where a synthetic quartz glass is to be used as an optical
member in an optical system employing a fluorine laser as a light source, it will
be an important subject to improve the transmittance.
[0006] Further, the optical system of an optical apparatus to be used for photolithography,
is constituted by a combination of many optical members such as lenses and prisms.
Accordingly, an improvement in transmittance of each individual optical member will
bring about a large improvement in transmittance when integrated as an entire optical
system.
[0007] However, heretofore, there has been no proposal for a method to improve the transmittance
in a region of wavelengths of not longer than 165 nm which is the wavelength region
of the fluorine laser or to produce a synthetic quartz glass for an optical member
having high transmittance efficiently and conveniently.
[0008] The present invention has an object to provide a process whereby a synthetic quartz
glass for an optical member having the transmittance in a region of wavelengths of
not longer than 165 nm improved, can be produced efficiently and conveniently.
[0009] The present invention further provides a synthetic quartz glass for an optical member
having a high transmittance at a wavelength of 157 nm and a method of using it.
DISCLOSURE OF THE INVENTION
[0010] The present invention provides a process for producing a synthetic quartz glass for
an optical member, which comprises a step of irradiating a synthetic quartz glass
having an OH group content of 50 ppm (weight ppm, the same applies hereinafter) or
lower with vacuum ultraviolet light having a wavelength of 180 nm or shorter to improve
the transmittance in a region of wavelengths of not longer than 165 nm.
[0011] Further, the present invention provides a synthetic quartz glass for an optical member
having an absorption coefficient of at most 0.70 cm
-1 at a wavelength of 157 nm.
[0012] Still further, the present invention provides a method of using a synthetic quartz
glass for an optical member, which is a method of using a synthetic quartz glass for
an optical member having an OH group content of 50 ppm or lower, and which comprises
a step of irradiating it with vacuum ultraviolet light having a wavelength of 180
nm or shorter before using it as an optical member.
BRIEF DESCRIPTION OF THE DRAWING
[0013]
Figure 1 is a graph showing the results of spectral transmittance measurements before
and after the irradiation treatment in Example 3 of the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0014] In the present invention, an optical member is one having a synthetic quartz glass
formed into a semiproduct or a product such as a lens for an exposure apparatus (such
as a projection system lens or illumination system lens), a prism (such as a beam
expander in a laser beam source), an etalon, a photomask, a photomask blank, a window
material or a spectral filter. Particularly, a lens, a photomask or a photomask blank
is preferred. Further, the above-mentioned exposure apparatus may, for example, be
an exposure apparatus for producing a semiconductor, LCD, a magnetic head or a printed
circuit board.
[0015] The present inventors have found that in order to improve the transmittance at a
wavelength of 165 nm or shorter of a synthetic quartz glass, if a synthetic quartz
glass having the OH group content and the hydrogen molecule content controlled, is
irradiated with vacuum ultraviolet light having a wavelength of 180 nm or shorter,
the transmittance at a wavelength of 165 nm or shorter can be improved.
[0016] Then, they have studied an influence of the OH group content and the hydrogen molecule
content in a synthetic quartz glass before the irradiation treatment (hereinafter
referred to as a "non-irradiated synthetic quartz glass") over the transmittance at
a wavelength of 165 nm or shorter of the synthetic quartz glass after the irradiation
treatment. As a result, it has been found that the OH group content in the non-irradiated
synthetic quartz glass gives an influence over the light transmittance in the vacuum
ultraviolet region, so that the light transmittance decreases as the OH group content
is high, but at a level of 50 ppm or lower, the transmittance at a wavelength of 165
nm or shorter can be improved by irradiation with vacuum ultraviolet light, and especially,
at a level of 30 ppm or lower (further at a level of 10 ppm or lower), such a content
is effective for the improvement of the transmittance at a wavelength of 165 nm or
shorter.
[0017] The mechanism for such improvement of the transmittance at a wavelength of 165 nm
or shorter, is not clearly understood, but may be considered as follows. There are
two type of states in which OH groups are present in the synthetic quartz glass. Namely,
in one state, they are present in an independent state, and in another state, they
are present in such a state that adjacent OH groups are hydrogen-bonded to one another.
The influence of the OH group content over the vacuum ultraviolet light transmittance
varies depending upon the state of OH groups, and the former state presents a larger
influence than the latter state. Namely, as compared with the transmittance of a synthetic
quartz glass which contains an equivalent amount of OH groups in an independent state,
the transmittance at a wavelength of 165 nm or shorter of a synthetic quartz glass
containing OH groups in a hydrogen-bonded state, is higher. It is considered that
most OH groups in a synthesized synthetic quartz glass are present usually in an independent
state without forming hydrogen bonds, and upon irradiation with light having a wavelength
of 180 nm or shorter, the state of OH groups changes into a hydrogen bond state, whereupon
the transmittance at a wavelength of 165 nm or shorter is improved.
[0018] Further, when the hydrogen molecule content in the synthetic quartz glass is at least
3×10
16 molecules/cm
3, the vacuum ultraviolet light transmittance can be improved with a smaller quantity
of ultraviolet ray irradiation. With respect to the effect for the improvement of
the transmittance, there is an optimum level of ultraviolet ray irradiation. If it
is too small, the transmittance will not be improved very much, and if it is too much,
defects will form, and the transmittance inversely decreases. Further, hydrogen molecules
in the synthetic quartz glass also have a function to suppress formation of defects
such as E' centers or NBOHC. When the hydrogen molecule content is at least 1×10
17 molecules/cm
3, such is effective for improvement of the transmittance at a wavelength of 165 nm
or shorter. Especially, when it is at least 1×10
18 molecules/cm
3, such is preferred from the viewpoint of the ultraviolet ray resistance (the nature
whereby the transmittance will not remarkably decrease by ultraviolet ray irradiation)
when it is used as a synthetic quartz glass for an optical member.
[0019] Further, in the present invention, the non-irradiated synthetic quartz glass preferably
contains substantially no reduction type defects. In the present invention, the reduction
type defects mean ≡Si-Si≡ and have an absorption band having a wavelength of 163 nm
at the center. The internal transmittance T
163 (%/cm) at 163 nm is assumed to be represented by the following formula (3) wherein
C
OH is the OH group content (ppm) in the synthetic quartz glass.

[0020] In the present invention, "contains substantially no reduction type defects" means
that the formula (3) relating to the internal transmittance at 163 nm is satisfied.
[0021] However, if reduction type defects are present, there will be an absorption band
with 163 nm at the center, whereby the actual transmittance (T
163) at the wavelength of 163 nm will be smaller than the value on the right side of
the formula (3). Therefore, "containing substantially no reduction type defects" is
effective to obtain a higher transmittance at a wavelength of 165 nm or shorter.
[0022] Further, fluorine may be contained in the non-irradiated synthetic quartz glass to
be used in the present invention. When fluorine is contained in the non-irradiated
synthetic quartz glass, fluorine is effective to reduce an instable structure in the
non-irradiated synthetic quartz glass and to improve the transmittance at a wavelength
of 165 nm or shorter. The fluorine content in the non-irradiated synthetic quartz
glass is preferably from 100 to 2000 ppm, more preferably within a range of from 100
to 600 ppm.
[0023] Metal impurities such as alkali metals, alkaline earth metals or transition metals,
in the non-irradiated synthetic quartz glass not only lower the transmittance at a
wavelength ranging from an ultraviolet region to a vacuum ultraviolet region but also
cause to lower the ultraviolet ray resistance, and therefore, their content is preferably
as small as possible. Specifically, the total amount of metal impurities is preferably
at most 100 ppb, particularly preferably at most 50 ppb.
[0024] In the present invention, the irradiation with vacuum ultraviolet light having a
wavelength of 180 nm or shorter is also effective to improve the transmittance in
a region of wavelengths of not longer than 165 nm by surface cleaning. The cleaning
effect can be evaluated as follows.
[0025] Namely, the cleaning effect is higher as the difference between T
a and T
b defined by the following formulae (1) and (2), becomes smaller. Here, R is the reflectance
of the synthetic quartz glass for an optical member at a wavelength of 157 nm, and
n is the refractive index of the synthetic quartz glass for an optical member at a
wavelength of 157 nm. T
b corresponds to the theoretical transmittance.

[0026] Among them, the reflectance R of the synthetic quartz glass at a wavelength of 157
nm can be obtained together with the absorption coefficient α at a wavelength of 157
nm by the following calculation formula (4) by measuring in vacuum the transmittance
T
c at a wavelength of 157 nm including a reflection loss, of at least three sheets of
the synthetic quartz glass having different thicknesses.
Tc: The transmittance at a wavelength of 157 nm including a reflection loss
R: The reflectance at a wavelength of 157 nm
α: The absorption coefficient at a wavelength of 157 nm (1/cm)
t: The thickness of the sample (cm)
[0027] The synthetic quartz glass for an optical member of the present invention is preferably
a synthetic quartz glass for an optical member, whereby the above difference between
T
a and T
b is at most 0.03, particularly preferably at most 0.01. Further, by bringing the above
difference between T
a and T
b to a level of at most 0.03 by irradiating a synthetic quartz glass for an optical
material having an OH group content of at most 50 ppm, with vacuum ultraviolet light
having a wavelength of 180 nm or shorter before using it as an optical member, the
synthetic quartz glass having a high transmittance at a wavelength of 165 nm or shorter,
can be used for various optical members.
[0028] In the present invention, the process for producing the non-irradiated synthetic
quartz glass is not particularly limited so long as it is a process whereby the OH
group content will be within the above-mentioned prescribed range. For example, a
direct method, a soot method (a VAD method, an OVD method) or a plasma method may
be mentioned. A soot method is particularly preferred from such a viewpoint that the
temperature during the production is low, and inclusion of impurities such as chlorine
and metals, can be avoided.
[0029] In the present invention, the wavelength of vacuum ultraviolet light to be irradiated
is 180 nm or shorter, preferably 175 nm or shorter. Further, the vacuum ultraviolet
light may be continuous light or monochromatic light.
[0030] The intensity of the vacuum ultraviolet light to be irradiated is preferably at least
1 mJ/cm
2. In order to obtain the effect in a shorter period of time, 5 mJ/cm
2 or higher is preferred. The irradiation time is suitably determined depending upon
the light source. If the total irradiation energy amount of ultraviolet light is too
small, the transmittance will not be substantially improved. On the other hand, if
it is too much, defects will form, and the transmittance may inversely decrease. Usually,
the total irradiation energy amount is preferably from about 300 to 50000 J/cm
2. The total irradiation energy amount is preferably at least 1000 mJ/cm
2, particularly preferably at least 3000 mJ/cm
2. If the hydrogen molecule content is high, even if the total irradiation energy amount
of ultraviolet light is large, defects tend to hardly form.
[0031] The atmosphere for irradiation treatment is preferably a nitrogen atmosphere or a
He atmosphere, since if oxygen molecules, moisture, etc. are contained in a large
amount in the atmosphere, they tend to absorb the vacuum ultraviolet light.
[0032] As a specific example of the vacuum ultraviolet light source, a xenon excimer lamp
(main wavelength: 172 nm) using xenon as a medium, or a fluorine laser (main wavelength:
157 nm) using fluorine as a medium, may, for example, be mentioned. In a case where
improvement of the transmittance at a wavelength of 165 nm or shorter is required
over a wide range, a xenon excimer lamp is preferred. Whereas, from the viewpoint
of the productivity, a fluorine laser is preferred.
[0033] In the present invention, the irradiation treatment may be carried out at any stage
before or after each step during the process for forming the synthetic quartz glass
into an optical member. Here, each step means, for example, a heating step, a cutting
step, a polishing step or a finishing step. The irradiation treatment may be carried
out after completion as the optical member. Further, the irradiation treatment may
be applied only to the light transmitting region (the region corresponding to the
light path for transmission of light). When the irradiation treatment is carried out
for the purpose of surface cleaning, it is preferred to carry out the irradiation
treatment before, particularly preferably immediately before, use as an optical member.
[0034] In the present invention, the synthetic quartz glass for an optical member preferably
has an absorption coefficient of at most 0.70 cm
-1 at a wavelength of 157 nm. More preferably, the absorption coefficient at a wavelength
of 157 nm is at most 0.30 cm
-1.
[0035] Further, it is preferably one having an infrared absorption peak attributable to
stretching vibration of a SiOH group at about 3640 cm
-1.
[0036] Now, the present invention will be described in further detail with reference to
Examples. However, the present invention is by no means restricted by these Examples.
EXAMPLE 1
[0037] Fine particles of quartz glass formed by heat hydrolysis in an oxyhydrogen flame
of SiCl
4, were deposited on a substrate by a known soot method, to prepare a porous quartz
glass body having a diameter of 35 cm and a length of 100 cm. The obtained porous
quartz glass body was set in an electric furnace capable of controlling the atmosphere,
and the pressure was reduced to 10 Torr at room temperature and maintained for 1 hour,
whereupon a mixed gas of He/SiF
4=99/1 (volume ratio) was introduced until the pressure became normal pressure. In
this atmosphere, fluorine doping was carried out by maintaining the system at normal
pressure and room temperature. Then, the temperature was raised to 1450°C in an atmosphere
of 100% He, and the system was maintained at this temperature for 5 hours to obtain
a fluorine-containing transparent glass body.
[0038] From the obtained transparent quartz glass body, a disc-shaped block of 100⌀ × 30
mm was cut out. The block was maintained for 250 hours in an atmosphere of 100% hydrogen
under 10 atm at 500°C to carry out hydrogen doping treatment to obtain a non-irradiated
synthetic quartz glass. The OH group content and the hydrogen molecule content of
the obtained synthetic quartz glass were 4.8 ppm and 17.4 × 10
17 molecules/cm
3, respectively. Further, by the above-mentioned formula (3), presence or absence of
reduction type defects was evaluated, whereby it was confirmed that substantially
no reduction type defects were contained.
[0039] Further, both sides of the disc-shaped synthetic quartz glass were subjected to optical
polishing, and then irradiation treatment was applied for 650 hours under a nitrogen
atmosphere by a xenon excimer lamp (main wavelength: 172 nm) (total irradiation energy
amount: about 13000 J/cm
2) to obtain a synthetic quartz glass for an optical member.
[0040] At that time, the absorption coefficient for ultraviolet light having a wavelength
of 157 nm ("the absorption coefficient for ultraviolet light having a wavelength of
157 nm" will be hereinafter referred to simply as "the absorption coefficient at a
wavelength of 157 nm") of the synthetic quartz glass before and after the irradiation
treatment, and the position (cm
-1) of the infrared absorption peak attributable to SiOH stretching vibration ("the
infrared absorption peak attributable to SiOH stretching vibration" will be hereinafter
referred to simply as the SiOH absorption peak) of the synthetic quartz glass after
the irradiation, were measured.
EXAMPLE 2
[0041] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 19 ppm and a hydrogen molecule content of 10.3 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared and irradiated
with a fluorine laser in a nitrogen atmosphere to obtain a synthetic quartz glass
for an optical member. The irradiation condition was 10 mJ/cm
2 × 40 Hz × 150 min. At that time, the absorption coefficient at a wavelength of 157
nm of the synthetic quartz glass before and after the irradiation treatment, and the
position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 3
[0042] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 31 ppm and a hydrogen molecule content of 2.1 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was carried out for 650 hours in a nitrogen atmosphere by an excimer lamp
using xenon as a medium (total irradiation energy amount: about 13000 J/cm
2) to obtain a synthetic quartz glass for an optical member. At that time, the absorption
coefficient at a wavelength of 157 nm of the synthetic quartz glass before and after
the irradiation treatment, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 4
[0043] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 33 ppm and a hydrogen molecule content of 0.8 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 650 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy amount: about 13000 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 5
[0044] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 54 ppm and a hydrogen molecule content of 32.5 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 1000 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy: about 20000 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 6
[0045] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 63 ppm and a hydrogen molecule content of 0.5 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 1000 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy: about 20000 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 7
[0046] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 5.2 ppm and a hydrogen molecule content of 17.4 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 75 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy amount: about 1500 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation treatment, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 8
[0047] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 12 ppm and a hydrogen molecule content of 10.3 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 75 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy amount: about 1500 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation treatment, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 9
[0048] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 32 ppm and a hydrogen molecule content of 0.8 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 75 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy amount: about 1500 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation treatment, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 10
[0049] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 5.2 ppm and a hydrogen molecule content of 17.4 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 35 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy amount: about 700 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation treatment, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
EXAMPLE 11
[0050] In the same manner as in Example 1, a non-irradiated synthetic quartz glass which
had an OH group content of 5.2 ppm and a hydrogen molecule content of 17.4 × 10
17 molecules/cm
3 and which contained substantially no reduction type defects, was prepared, and irradiation
treatment was applied for 300 hours in a nitrogen atmosphere by a xenon excimer lamp
(total irradiation energy amount: about 6000 J/cm
2). At that time, the absorption coefficient at a wavelength of 157 nm of the synthetic
quartz glass before and after the irradiation treatment, and the position (cm
-1) of the SiOH absorption peak of the synthetic quartz glass after the irradiation,
were measured.
Evaluation method
[0051] From the center portion of the obtained block of the synthetic quartz glass for an
optical member, a sample for evaluation of 30⌀ × 10 mm, was cut out and polished.
Then, the hydrogen molecule content, the OH group content, the SiOH absorption peak
and the absorption coefficient at a wavelength of 157 nm, were obtained by the following
methods.
[0052] Hydrogen molecule content) Raman spectrometry was carried out, and the hydrogen molecule
content (molecules/cm
3) was obtained from the intensity ratio (=I
4135/I
800) of the intensity I
4135 detected from the scattering peak at 4135 cm
-1 of the laser Raman spectrum to the intensity I
800 of the scattering peak at 800 cm
-1 representing the fundamental vibration between silicon and oxygen (V.S. Khotimchenko
et a., Zhurnal Prikladnoi Spektroskopii, 46(6), 987-997 (1986)).
[0053] OH group content and Si-OH absorption peak) If a common synthetic quartz glass contains
OH groups, a peak at 3673 cm
-1 will appear in the transmission spectrum by the infrared spectroscopy. From the absorption
of this peak, the substantial peak height (H) is obtained, and further, the thickness
(L, unit: cm) of the synthetic quartz glass, through which infrared light passes during
the measurement, is obtained, whereupon the OH group content s obtained from the following
formula.

[0054] This technique is called β-OH and is commonly used to obtain the OH group content
in glass (for example, J.P. Wiiliams et al., Ceram.Bull., 55(5), 524 (1976)).
[0055] Absorption coefficient at a wavelength of 157 nm) Using a vacuum ultraviolet spectrophotometer,
the transmittances at a wavelength of 157 nm of a sample having a thickness of 10
mm and a sample having a thickness of 2 mm were measured, and from these transmittances,
the absorption coefficient at a wavelength of 157 nm was calculated. The smaller the
value of the absorption coefficient at a wavelength of 157 nm, the higher the transmittance.
The results of measurements of spectrum transmittance before and after the vacuum
ultraviolet light irradiation treatment in Example 3, are shown in figure 1.
[0056] The evaluation results of Examples 1 to 11 are summarized in Table 1. Examples 5
and 6 are examples wherein the absorption coefficients at a wavelength of 157 nm are
large, since the OH group contents are large. Further, Example 4 is an example wherein
the total irradiation energy amount of ultraviolet light was large in spite of a small
hydrogen molecule content, whereby defects formed, and the absorption coefficient
at a wavelength of 157 nm increased by ultraviolet light irradiation.
Table 1
| Example |
OH group content (ppm) |
Hydrogen molecule content (×1017 molecules/cm3) |
Absorption coefficient at a wavelength of 157 nm |
SiOH absorption peak |
| |
|
|
Before irradiation |
After irradiation |
|
| 1 |
4.8 |
17.4 |
0.223 |
0.196 |
3642 |
| 2 |
19 |
10.3 |
0.565 |
0.293 |
3641 |
| 3 |
31 |
2.1 |
0.787 |
0.574 |
3643 |
| 4 |
33 |
0.8 |
0.821 |
0.831 |
3673 |
| 5 |
54 |
32.5 |
1.146 |
0.976 |
3642 |
| 6 |
63 |
0.5 |
1.272 |
1.742 |
3643 |
| 7 |
5.2 |
17.4 |
0.230 |
0.171 |
3640 |
| 8 |
12 |
10.3 |
0.485 |
0.292 |
3641 |
| 9 |
32 |
0.8 |
0.811 |
0.697 |
3640 |
| 10 |
5.2 |
17.4 |
0.240 |
0.203 |
3648 |
| 11 |
5.2 |
17.4 |
0.240 |
0.186 |
3640 |
EXAMPLES 12 to 16
[0057] With respect to the synthetic quartz glass having an OH group content of 1.5 ppm,
five samples were prepared for each of four different sizes differing in the thickness
i.e. 25 mm⌀ × 2 mm in thickness, 25 mm⌀ × 10 mm in thickness, 25 mm⌀ × 20 mm in thickness
and 25 mm⌀ × 30 mm in thickness. With respect to each sample, the opposing two surfaces
of 25 mm⌀ were mirror-polished with a precision of a surface roughness of at most
5 Å and a parallel plane degree of at most 10 seconds. These samples were wet-washed
in the following order.
1) Immersed for 10 minutes in a mixed liquid (liquid temperature: 100°C) in a ratio
of sulfuric acid:aqueous hydrogen peroxide solution:water = 1:1:8.
2) Subjected to running water rinsing for 5 minutes with deionized water.
3) Immersed for 10 minutes in a mixed liquid (liquid temperature: 25°C) in a ratio
of ammonia:aqueous hydrogen peroxide solution:water = 1:1:8.
4) Subjected to running water rinsing for 5 minutes with deionized water.
5) Subjected to ultrasonic cleaning for 10 minutes with deionized water (liquid temperature:
40°C)
6) Flon vapor drying
[0058] Then, the sample was irradiated with a xenon excimer lamp light (illumination intensity:
10 mW/cm
2) in a nitrogen gas atmosphere under the conditions as shown in Table 2 to carry out
cleaning for various irradiation times. After dry system cleaning, the sample was
immediately set in a vacuum ultraviolet spectrophotometer (UV201M, manufactured by
Bunko Keiki), and the transmittance at a wavelength of 157 nm was measured in a nitrogen
atmosphere. By inserting the transmittance T
1, T
2, T
3 or T
4 at a wavelength of 157 nm of a sample having a thickness of 2 mm (=t
1), 10 mm (=t
2), 20 mm (=t
3) or 30 mm (=t
4), obtained by the measurement, the reflectance R at a wavelength of 157 nm and the
absorption coefficient α at a wavelength of 157 nm were obtained by a least squares
method.

(i=1, 2, 3, 4)
Ti: Transmittance at a wavelength of 157 nm including reflection loss
R: Reflectance at a wavelength of 157 nm
α: absorption coefficient at a wavelength of 157 nm (1/cm)
ti: Thickness of the sample (cm)
[0059] Using the reflectance R at a wavelength of 157 nm, thus obtained, the transmittance
T
a was obtained by the formula (1), and the difference

from the theoretical transmittance T
b (=0.884) calculated by the formula (2) from the refractive index n (=1.661) at a
wavelength of 157 nm, was obtained, whereby the cleaning degree of the surface was
evaluated. The results are shown in Table 2.
Table 2
| |
Example 12 |
Example 13 |
Example 14 |
Example 15 |
Example 16 |
| Irradiation time |
No irradiation |
3 min |
10 min |
30 min |
60 min |
| T1 |
80.0 |
83.8 |
86.0 |
86.2 |
86.4 |
| T2 |
73.7 |
77.3 |
79.3 |
79.5 |
79.7 |
| T3 |
66.6 |
69.9 |
71.8 |
71.9 |
72.0 |
| T4 |
60.2 |
63.2 |
65.0 |
65.0 |
65.1 |
| α |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
| R |
0.101 |
0.079 |
0.065 |
0.064 |
0.063 |
| Ta |
0.817 |
0.855 |
0.878 |
0.880 |
0.881 |
| ΔT |
0.067 |
0.029 |
0.006 |
0.004 |
0.003 |
INDUSTRIAL APPLICABILITY
[0060] According to the present invention, a synthetic quartz glass for an optical component
having an improved transmittance at a wavelength of 165 nm or shorter, can be produced
highly efficiently and conveniently.